Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
  • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines

Definitions

• R stands for alkyl
• R stands for vinylene, phenylene, naphthylene or another polynuclear ring system
• Y stands for the group S and S e (wherein 5 stands for halogen or 804R.) N-NO,:NC6H5 or another reactive bivalent atom grouping.
• the compounds of Formula 1 have in a-position to the N-atom, a side chain containing sulfur or selenium, said compounds may be equally well represented as a salt consisting of an acid radical and a radical of the formula a lkyl in which case Z is S or Se, and X is the remainder of a heterocyclic system of the type used in cyanine dyes, for instance, the residue of the system wherein A is phenylene.
• the reactive methyl group may also stand in para-position to the nitrogen in the case of the bases derived from pyridine. Furthermore there may be used the pseudo bases resulting from the quaternary ammonium salts by splitting off hydrogen halide.
• the reaction is carried out in presence of condensation agents or solvents.
• condensation agents are the pyridine bases mixtures of pyridine bases, for instance, pyridine and piperidine, alcohol and piperidine, monoethylamine and other strong organic bases, and sodium ethylate.
• the yield obtained by the present process is far superior to that obtained by the process according to Mills and Braunholtz (cf. Journ. Chem. Soc. London, 123, 2804-13, 0.1924/11383).
• the dyes are obtained in a very pure form. They may be crystallized directly from the reaction mixture without by-products, or they may be precipitated by means of water.
• the nitrosoimido group reacts with the reactive methyl group of the heterocyclic bases under separation of nitrogen and water.
• the cyanine dyestuffs prepared according to this invention are applicable for sensitizing photographic silver halide emulsions.
• the sensitizing may be effected in the manner well known 55 in the ar
• the following examples illustrate the invention:
• the alcoholic solution of the dye has an absorption maximum at a wave length of about 415mb.
• Both dyestuffs are obtainable with an equally good yield, by using an alcoholic or an aqueous alcoholic solution and adding thereto an amount of caustic alkali, piperidine or pyridine which slightly surpasses 1 molecular proportion of the respective substance.
• the alcoholic solution of the dye has an absorption maximum at a wave length of about 490,LL/L.
• the alcoholic solution of the dye has an absorption maximum at a wave length of about 492 l.
• the alcoholic solution of the dye has an absorption maximum at a wave length of about 495 EXAMPLE 6.
• [3 ethyl benethiazole -(2) ]-[1 ethyl-quinoline- (2) l-methinecyanine iodide 2 grams of 2-methylbenzothiazole ethiodide (more than one molecular proportion) and 2 grams of N-ethyl-a-seleno-ethiodide-quinolon (one molecular proportion) are dissolved in 200 cc. of hot alcohol. To this mixture there are added drop by drop 2.5 cc. of piperidine. When cooling, the reddish yellow dyestufi is precipitated.
• the reaction takes the following course:
• the alcoholic solution of the dye has an absorption maximum at a wave length of about 492 EXAMPLE 7.[3-ethg/l-benzo:co-(2) ]-[1 -ethyZ-6- methyl-quinoline- (2) l-methinecyanine iodide corresponding with the formula cooled and the dye separates in form of a thick orange yellow crystalline mass (eventually after rubbing the wall of the vessel with a glass rod or after introduction of a crystal nucleus). The crystals are filtered and washed with alcohol and ether. After recrystallizing two times from alcohol the yield amounts to 19 grams of pure dyestuff from 25 grams of raw dyestuif.
• the alcoholic solution of the dye has an absorption maximum at a wave length of about 460/.L/L.
• EXAMPLE 8 [Ii-ethyl benzseZenazole-(Z) ]-[1- ethyl 6 methyl-quinoline-(z) l-methinecyanine iodide corresponding with the formula C211 ozHs may be obtained by dissolving 100 grams of 2-methylbenzoselenazole ethiodide in 1 liter of alcohol while heating under reflux on the steam bath. Hereon there are added 110 grams of N-ethyl-para-tolu-a-thio-ethiodide-quinolon and after a short boiling and complete dissolution 40 cc. of piperidine are slowly entered. The dye is immediately precipitated as a thick crystalline mass. The mass is still heated on the steam bath for hour, then it is cooled and the dye is filtered. After recrystallizing two times from alcohol the dye is pure.
• the yield amounts to grams of raw dyestuff and 75' grams of pure dyestufi.
• the alcoholic solution of the dye has an absorption maximum at a wave length of about 500,Li .t.
• EXAMPLE 9 [1-ethyl-quinoline-(4) [Z-ethyl- 6 -.methyl quinoline (2) l methinecyanine iodide corresponding with the formula may be obtained by mixing 31 grams A mol) of lepidine ethiodide, 38 grams A mol) of N ethyl para-tolu-a-thio-quinolone ethiodide and 200 cc. of pyridine and boiling the mixture. Then there are added 1.0 cc. of piperidine and after boiling for 5 minutes the mixture is cooled and mixed with cc. of dry ether. If the dye does not separate it will be precipitated on rubbing the wall of the vessel with a glass rod. The dye which has separated after 1 hours standing is filtered and recrystallized two times from alcohol.
• the yield is 24 grams of raw dyestuil and 20 grams of pure dyestufi.
• the alcoholic solution of the dye has two absorption maxima at wave lengths of about 5651/41. and 525ml.
• EXAMPLE l0.[3-ethyl-anthracenethiazole- (2) l- [1- ethyl 6 methyl-quinoline- (2) l-methinecyanine iodide corresponding with the formula may be obtained by mixing 10 grams of N-ethylpara-tolu-a-thio-ethiodide-quinolon, 10 grams of 2-methyl-p-anthrathiazole ethiodide and '15 cc. of pyridine and boiling the mixture. The condensation takes place immediately and is completed by the addition of 1 cc. of piperidine.
• Boiling is continued for 5 minutes and then the mixture is cooled.
• the greatest part of the red dye separates on cooling and is removed by filtration. From the pyridine solution there may be obtained a further small quantity of dyestuif by precipitation with ether.
• the dye is recrystallized from a large quantity of methanol and may be if required made into the more soluble nitrate by means of silver nitrate.
• the yield of dyestufl amounts to about 22 per cent calculated on the Z-methylanthrathiazole ethiodide.
• the alcoholic solution of the dye has an absorption. maximum at a wave length of about 595 144.
• EXAMPLE l1 [3-methyl-benzthiaz0le- 2) 1- [1 ethyl quinoline- (4) l-methinecyanine iodide ethiodide corresponding with the formula may be ma by b iling a mixture of 14 gra s o p d e ethiodide and 35 9f p d ne d adding 10 grams of N-methylthiobenzothiazolonemethiodide in three portions. Boiling is continued for 1 minute and then there are added 1 10 drops of piperidine. After further boiling for 2 minutes the mixture is cooled and the greatest part of it crystallizes and is filtered. A further quantity of dye may be obtained on the addition of ether to the pyridine solution.
• the yield of raw product amounts to 35 per cent and the quantity of pure product amounts to 30 per cent of dye.
• the alcoholic solution of the dye has an ab with 2-methylbenzoselenazole ethiodide in alcohol until dissolution occurs, adding piperidine to the boiling mixture and separating the formed dye.
• a process for the preparation of a cyanine salt comprising condensing, in the presence of a basic condensing agent, a salt consisting of an acid radical and a radical of the following formula:
• A represents a phenylene group and R represent alkyl groups, with a cyclammonium alkyl quaternary salt containing a reactive methyl group and selected from the group of cyclammonium alkyl quaternary salts consisting of those of the quinoline series, the thiazole series and the oxazole series.
• a process for the preparation of a cyanine salt comprising condensing, in the presence of a basic condensing agent, a salt consisting of an acid radical and a radical of the following formula:
• R represents alkyl groups, with a cyclammonium alkyl quaternary salt of the quinoline series containing a reactive methyl group.
• a process for the preparation of a cyanine salt comprising condensing, in the presence of a basic condensing agent, a salt consisting of an acid radical and a radical of the following formula:
• A represents a phenylene group and R represents alkyl groups, with a cyclammonium alkyl quaternary salt of the thiazole series containing a reactive methyl group.
• a process for the preparation of a cyanine salt comprising condensing, in the presence of a basic condensing agent, a salt consisting of an acid radical and a radical of the following formula:
• A represents a phenylene group and R represents alkyl groups with a cyclammonium alkyl quaternary salt of the quinoline series containing a reactive methyl group.
• alkyl wherein X is the remainder of a heterocyclic system of the type used in cyanine dyes and Z is a member of the class consisting of S and Se, with a cyclammonium alkyl quaternary salt of the type used in cyanine dyes and containing a reactive alkyl group on the heterocyclic ring.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Plural Heterocyclic Compounds (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
• Indole Compounds (AREA)
• Thiazole And Isothizaole Compounds (AREA)

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Cited By (1)

• 0
  • BE BE397525D patent/BE397525A/xx unknown
• 1933
  • 1933-07-06 US US679264A patent/US2292021A/en not_active Expired - Lifetime
  • 1933-07-07 GB GB19305/33A patent/GB423792A/en not_active Expired
  • 1933-07-10 FR FR758198D patent/FR758198A/fr not_active Expired

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